The Journal of Organic Chemistry
Article
then filtered, and the solid was washed with heptane−toluene (1:2, 4 ×
(7) Motti, E.; Della Ca, N.; Xu, D.; Piersimoni, A.; Bedogni, E.; Zhou,
Z.-M.; Catellani, M. Org. Lett. 2012, 14, 5792−5795.
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20 mL) to give (S)-6 as a white, granular solid (17.3 g, 86%, 99.6%ee
(S)). Evaporation of the liquors gave a brown foam (2.41 g). Analysis
showed the product 6 present in this fraction to have an enantiomeric
2
5
excess of 87.2% (S). mp 119−120 °C; [α] −23.2° (c = 1.0, THF).
D
1
,11,12
Sample from known route using (−)-DIP-Cl
(99.8% ee) −24.4°
(9) Sakakura, A.; Kawajiri, K.; Ohkubo, T.; Kosugi, Y.; Ishihara, K. J.
Am. Chem. Soc. 2007, 129, 14775−14779.
(
c = 1.0, THF); IR (KBr) 3366, 1507, 1595, 1497, 1442, 1407, 1310,
160, 1144, 1066, 966, 926, 670, 831, 759, and 692 cm . H NMR
−1 1
1
(10) (a) Melpolder, J. B.; Heck, R. F. J. Org. Chem. 1976, 41, 265.
(
1
400 MHz, CDCl , 18 °C) δ = 8.08 (d, J = 8.4 Hz, 1H), 8.06 (d, J =
3
(b) Chalk, A. J.; Magennis, S. A. J. Org. Chem. 1976, 41, 273−278.
.6 Hz, 1H), 7.71 (s, 1H), 7.67 (d, J = 8.8 Hz, 1H), 7.63 (s, 1H), 7.61
(11) King, A. O.; Corley, E. G.; Anderson, R. K.; Larsen, R. D.;
(
d, J = 8.8 Hz, 1H), 7.50 (d, J = 7.2 Hz, 1H), 7.43 (dd, J = 8.8, 2.0 Hz,
Verhoeven, T. R.; Reider, P. J.; Xiang, Y. B.; Belley, M.; Leblanc, Y.;
1
7
3
1
H), 7.38−7.30 (m, 4H), 7.26 (td, J = 7.2, 1.6 Hz, 1H), 7.22 (td, J =
.3, 1.4 Hz, 1H), 7.14 (td, J = 7.4, 2.0 Hz, 1H), 4.74−4.70 (m, 1H),
.3 (br s, 1 H), 3.28−3.20 (m, 2H), 3.16−3.10 (m, 1H), 2.5 (br s,
Labelle, M.; Prasit, P.; Zamboni, R. J. J. Org. Chem. 1993, 58, 3731−
3
735.
(
12) Shinkai, I.; King, A. O.; Larsen, R. D. Pure Appl. Chem. 1994, 66,
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1
H), 2.17−2.10 (m, 2H), 1.70 (s, 3H) and 1.67 (s, 3H) ppm. H
1
NMR (400 MHz, C D , 18 °C) δ = 8.46 (d, 1H, J = 1.6 Hz),8.01 (d,
6
6
(
1
7
1
2
H, J = 16.4 Hz), 7.79 (s, 1H), 7.53−7.46 (m, 3H), 7.38 (d, 1H, J =
.6 Hz), 7.33 (d, 1H, J = 8.0 Hz), 7.30−7.13 (m, 7H), 4.75−4.71 (m,
H), 3.46−3.38 (m, 1H), 3.26−3.20 (m, 1H), 3.03 (br s, 1H), 2.25−
Guay, D. U.S. Patent 5,565,473, 1996. (b) Belley, M. L.; Leger, S.; Roy,
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.19 (m), 2.03 (br s, 1H), 1.54 (s, 3H) and 1.53 (s, 6H) ppm; 13
C
(14) (a) Liang, J.; Lalonde, J.; Borup, B.; Mitchell, V.; Mundorff, E.;
NMR (100 MHz, CDCl , 18 °C) δ = 156.9, 148.5, 145.4, 145.0, 140.2,
3
Trinh, N.; Kochrekar, D. A.; Cherat, R. N.; Pai, G. G. Org. Process. Res.
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1
1
3
1
1
1
36.2, 136.1, 135.5, 135.2, 131.4, 128.8, 128.6, 128.4, 128.1, 127.2,
27.0, 126.4, 126.3, 126.0, 125.6, 125.5, 124.7, 119.5, 74.1, 72.9, 41.9,
2.1, 32.0, and 29.6 ppm; 13C NMR (100 MHz, C D , 18 °C) δ =
6
6
57.2. 149.2, 146.4, 145.8, 140.7, 136.8, 135.9, 135.7, 135.6, 131.8,
29.0, 128.9, 128.7, 128.6, 127.9, 127.9, 127.5, 126.9, 126.9, 126.4,
26.0, 125.8, 120.1, 125.5, 74.0, 73.0, 42.6, 32.2, 32.1, and 30.1 ppm.
(
d) Shafiee, A.; Motamedi, H.; King, A. Appl. Microbiol. Biotechnol.
1998, 49, 709−717.
15) (a) Fuji, A.; Hashiguchi, S.; Uematsu, N.; Ikariya, T.; Noyori, R.
37
+
35
+
m/z ES 460 ([M Cl + H] , 40), 458 ([M Cl + H] , 100).
(
J. Am. Chem. Soc. 1996, 118, 2521−2522. (b) Avdagic, A.; Mohar, B.;
ASSOCIATED CONTENT
Supporting Information
■
Sterk, D.; Stephan, M. PCT Patent Application WO/2006/008562,
*
S
2
(
006.
16) (a) McGarrity, J.; Bappert, E.; Belser, E. PCT Patent Application
.
Method of chiral analysis for 6, and NMR spectra of 6, 9,
0b, 10c, 11b, 11c, 12, and 13. Reaction conditions employed
WO/2008/131932, 2008. (b) Abdur-Rashid, K.; Jia, W.; Lu, S.; Guo,
R.; Chen, X.; Amoroso, D. PCT Patent Application WO 2012031358,
1
2
012.
(17) (a) Ohkuma, T.; Koizumi, M.; Doucet, H.; Phang, H. T.;
Kozawa, M.; Murata, K.; Katayama, E.; Yokozawa, T.; Ikariya, T.;
Noyori, R. J. Am. Chem. Soc. 1998, 120, 13529−13530. (b) Noyori, R.;
Ohkuma, T. Angew. Chem. Int. Ed. 2001, 40, 40−73. (c) Burk, M. J.;
Hems, W.; Herzberg, D.; Malan, C.; Zanotti-Gerosa, A. Org. Lett.
AUTHOR INFORMATION
Notes
■
*
2
000, 2, 4173−4176. (d) Henschke, J. P.; Burk, M. J.; Malan, C. G.;
Herzberg, D.; Peterson, J. A.; Wildsmith, A. J.; Cobley, C. J.; Casy, G.
Adv. Synth. Catal. 2003, 345, 300−307. (e) Chaplin, D.; Harrison, P.;
Henschke, J. P.; Lennon, I. C.; Meek, G.; Moran, P.; Pilkington, C. J.;
Ramsden, J. A.; Watkins, S.; Zanotti-Gerosa, A. Org. Process. Res. Dev.
2003, 7, 89−94. (f) Wu, J.; Ji, J.-X.; Guo, R.; Yeung, C.-H.; Chan, A. S.
C. Chem.Eur. J. 2003, 9, 2963−2968. (g) Xie, J.-H.; Wang, L.-X.;
Zhu, S.-F.; Fan, B.-M.; Duan, H.-F.; Zhou, Q.-L. J. Am. Chem. Soc.
2003, 125, 4404−4405. Nara, H.; Yokozawa, T. PCT Patent
ApplicationWO 2011/135753 A1, 2011.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
We are grateful to the management of Dr. Reddy’s Laboratories
Limited for supporting this project.
■
REFERENCES
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